Comment on the relation between the nonadiabatic coupling and the complex intersection of potential energy curves

Abstract

Simple relations are discussed that provide a correspondence between the complex intersection of two potential surfaces and the nonadiabatic coupling matrix element between those surfaces. These are key quantities in semiclassical and quantum mechanical theories of collision-induced electronic transitions. Within the two-state approximation, the complex intersection is shown to be directly related to the location and magnitude of the peak in the nonadiabatic coupling. Two cases have been considered: (i) the avoided crossing between two potential surfaces, and (ii) the spin—orbit interaction due to a 2P halogen atom. Comparisons are made between the results of the two-state model and the results of ab initio quantum chemical calculations.